CN1050056A - The production method of sodium hydroxide lye - Google Patents

The production method of sodium hydroxide lye Download PDF

Info

Publication number
CN1050056A
CN1050056A CN 90107940 CN90107940A CN1050056A CN 1050056 A CN1050056 A CN 1050056A CN 90107940 CN90107940 CN 90107940 CN 90107940 A CN90107940 A CN 90107940A CN 1050056 A CN1050056 A CN 1050056A
Authority
CN
China
Prior art keywords
sodium
sodium hydroxide
solution
amalgam
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 90107940
Other languages
Chinese (zh)
Inventor
让·韦拉滕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Publication of CN1050056A publication Critical patent/CN1050056A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04—Hydroxides
    • C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
    • C01D1/22—Preparation by reacting oxides or hydroxides with alkali metal salts with carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C25B1/42—Decomposition of amalgams

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The production method of sodium hydroxide lye, root accordingly, sodium amalgam is to be decomposed by the water medium that is dissolved with sodium hydroxide that the lime treatment aqueous sodium carbonate produces.

Description

The production method of sodium hydroxide lye
The present invention relates to a kind of method of producing aqueous NaOH alkali lye.
A kind of currently known methods of producing aqueous NaOH alkali lye is arranged, in this method sodium chloride aqueous solution in the electrolyzer of mercury cathode by electrolysis, after sodium amalgam (contacting with the parts made from graphite or carbon) is discharged by the bottom of electrolyzer, decompose (J.S.Sconce with water treatment, " Chlorine, its manufacture, Properties and uses " Reinhold Publishing Corporation, 1962, Pages 127 to 199).In this known method, the sodium chloride aqueous solution electrolysis produces chlorine, produces hydrogen subsequently with the water decomposition amalgam and produces aqueous sodium hydroxide solution, is commonly referred to aqueous NaOH alkali lye.Therefore, the production of sodium hydroxide relates to the production of following of chlorine inevitably, and its productive rate is the chlorine of per kilogram sodium hydroxide 886 grams.This fixed relationship between the corresponding output with sodium hydroxide of chlorine has formed the main drawback of this production method, and the result makes this method can not provide the handiness of necessity so that its output adapts to the fluctuation in chlorine and sodium hydroxide market respectively.
In addition, also having a kind of known method is electrolytic process coupling in the electrolyzer of selecting the perviousness cationic membrane with mercury utmost point electrolytic tank electrolysis method and sodium chloride solution.In this known method, the sodium amalgam that is produced by the mercury electrolyzer is (US-A-3,321,388) of finishing decomposition by the dilute sodium hydroxide aqueous solution that produces in the ion-exchange membrane electrolyzer.This currently known methods has improved the total recovery of two electrolyzers really, but fails to overcome shortcoming noted earlier, promptly can not follow to produce with chlorine about the production of sodium hydroxide to have nothing to do.
The object of the present invention is to provide a kind of method that can overcome the prior art shortcoming, make its electrolysis production that can control sodium hydroxide, and follow production irrelevant with chlorine.
Therefore, the present invention relates to produce the method for sodium hydroxide lye,, decompose sodium amalgam with the water medium that is dissolved with sodium hydroxide according to this method; According to the present invention, the sodium hydroxide of use is produced by the lime treatment aqueous sodium carbonate.
The method according to this invention, the sodium hydroxide lye representative is a kind of with the resulting aqueous sodium hydroxide solution of water decomposition sodium amalgam.
Sodium amalgam is the alloy of mercury and sodium, and normally electrolysis obtains in mercury-cathode cell by sodium chloride aqueous solution.In general, implement method of the present invention, the sodium content of amalgam is not very strict.Yet in fact the good operation of mercury electrolyzer relates to the sodium content of restriction in the amalgam and will be lower than 7 gram/kilograms.Best concentration is the sodium that per kilogram mercury contains the 1-5 gram.
According to the present invention, decompose amalgam by the water medium that contains sodium hydroxide that obtains with the lime treatment aqueous sodium carbonate.Water medium generally is a water.It is well-known technology (K.Winaker and L.K ü chler, " Technologie minerale " translated by A.Zundel, Eyrolles Publishers that aqueous sodium carbonate and lime reaction are produced sodium hydroxide; 1962, Pages 382 to 388).This technology of causticization yellow soda ash causes obtaining aqueous sodium hydroxide solution, and is used for handling amalgam.
The sodium carbonate solution that the method according to this invention, working concentration are high as far as possible is favourable, preferably saturated solution.Sodium carbonate solution can be obtained by any appropriate means.Employed solution normally produce by removing in sodium bicarbonate aqueous solution or the suspension by sodium bicarbonate.For example, in the method for producing soda with ammoniacal liquor, just can obtain this solution (Te Pang Hou, " Manufacture of Soda ", Hafner Publishing Company, 1969).Removing sodium bicarbonate from sodium bicarbonate aqueous solution or suspension is a kind of well-known operative technique, comprises heating usually, for example heats with vapour stream.
Within the scope of the invention, lime is calcium oxide or calcium hydroxide.Preferably use the aq suspension of calcium hydroxide.
In a specific embodiment of the inventive method, use the lime treatment aqueous sodium carbonate, from reaction mixture, collect rare aqueous sodium hydroxide solution then, described dilute solution must be evaporated under controlled conditions, to generate the concentrated solution that per kilogram contains the above sodium hydroxide of 186 grams, described concentrated solution goes out the sodium hydroxide hydrate through cooling crystallization from mother liquor, collects the sodium hydroxide hydrate, be heated to enough temperature and make it fusing, handle sodium amalgam with the sodium hydroxide hydrate of fusing.According to this embodiment of the inventive method, the sodium hydroxide hydrate of fusing constitutes the aforementioned water medium that is used to decompose sodium amalgam
According to this embodiment of the inventive method of just having described, the dilute sodium hydroxide aqueous solution of collecting from the reaction of lime and yellow soda ash generally contains just like 5-25%(by weight) sodium hydroxide, be generally 8-15% most.Usually it is stain by the dissolved substance that used reactant in the causticizing reaction (yellow soda ash and lime) produces, and is particularly produced by yellow soda ash, sodium-chlor and sodium sulfate.According to the present invention, it must be through evaporation concentration controlledly so that its dissolved sodium hydrate content be higher than 186.0g/kg and be preferably lower than 743g/kg, on the one hand, these content are respectively corresponding to the content of the ice and the eutectic mixture of seven hydronium(ion) oxidation sodium, on the other hand corresponding to compound N aoH and NaoH.1H 2The content of the eutectic mixture of O.From evaporation, collect and make behind the concentrated solution it be cooled to that crystallization goes out hydration sodium hydroxide in the mother liquor.Cooling temperature depends on the concentration of the concentrated sodium hydroxide solution of collecting from evaporation, and is easily NaoH-H 2The O system phase diagram is determined (P.Pascal, " Nouveau trait é de chimie min é rale ", Volume II, First part, Masson et Cie, publishers, 1966, pages 254 to 258).In this embodiment of the inventive method, use the technology described in document US-A-1733879.In order to collect the sodium hydroxide hydrate, can use any can be from mother liquor with its isolating method, for example filtration, sedimentation or centrifuging.
This embodiment of the inventive method, the advantage that has is to avoid the aforementioned existence that is used for decomposing the water medium impurity of sodium amalgam.
In above-mentioned another advantageous embodiments of the inventive method, the evaporation of control dilute solution is so that make the concentrated aqueous solution of per kilogram contain the sodium hydroxide of about 468-321 gram, and on the one hand, such concentration is respectively corresponding to compound N aoH3.5H 2O and NaOH2H 2The eutectic mixture concentration of O, on the other hand, corresponding to the concentration of the saturated aqueous solution of sodium hydroxide under this eutectic temperature.When finishing this alternative embodiment of the inventive method, hope spissated aqueous solution naoh concentration of collection from evaporation obviously is different from 388.3 gram/kilograms and (is equivalent to specific compound NaoH3.5H 2O), so that in the crystallisation by cooling process, make the easier mother liquor that enters of impurity.Consider that from economic angle preferably the concentrated solution naoh concentration of collecting is lower than 388.3 gram/kilograms from evaporation.
In another embodiment of the inventive method of just having described, finish concentrated solution refrigerative temperature range, on the one hand, at compound N aoH3.5H 2O and NaoH2H 2The solidification value of the eutectic mixture of O (about 5 ℃) is specific compound NaOH3.5H on the other hand 2The fusing point of O (about 16 ℃).
The inventive method allows the mercurous electrolyzer of flexible operating, makes electrolytic cell operation might adapt to the market of sodium hydroxide, and does not influence the output of chlorine.
Feature of the present invention and details will show by the description of an accompanying drawing, and accompanying drawing shows the full-scale plant synoptic diagram that uses the inventive method specific embodiments.
Full-scale plant shown in the figure comprises sodium carbonate causticization unit and electrolysis cells.
In the causticization unit, the aqueous solution of yellow soda ash 2 and unslaked lime 3 is sent into reaction chamber 1.The aqeous suspension of collecting from reaction chamber 14 mainly contains the lime carbonate that is suspended in the aqueous sodium hydroxide solution.Suspension 4 is handled in the settling pocket 5 of collecting precipitation of calcium carbonate 6 and rare aqueous sodium hydroxide solution 7 respectively.Usually precipitation 6 contains a large amount of calcium hydroxide.Second reaction chamber 8 that it is sent to is also sent into aqueous sodium carbonate 9 in addition.Separate wherein insoluble matter 11 after strainer 10 is handled, the aqueous solution 12 is recycled in the reaction chamber 1.The solution of being collected by settling pocket 57 contains 8-15%(for example by weight) sodium hydroxide.In addition, it is also stain by many dissolved impurities especially sodium sulfate, yellow soda ash and sodium-chlor.Solution 7 is sent to vaporizer 13 and concentrates content up to sodium hydroxide between 321-388.3 gram/kilogram.Evaporation causes the removal of water 14 and the precipitation of partial impurities, mainly is sodium sulfate and yellow soda ash, and these are all removed 15.Handled in water cooler 17 by the concentrated aqueous solution 16 that vaporizer 13 is collected, cooling temperature goes out compound N aOH3.5H in order to crystallization from mother liquor between 5～16 ℃ 2O.Collect crystalline compounds 18 and mother liquor 30 respectively.Crystalline compounds 18 is to be NaoH3.5H by molecular formula basically 2The sodium hydroxide hydrate of O is formed.It is heated to the above temperature of its fusing point (15.9 ℃) after being sent to storage room 19 once more, and for example room temperature contains the 388.3 gram aqueous sodium hydroxide solutions 20 of having an appointment so that can obtain per kilogram.Mother liquor 30 is a kind of aqueous sodium hydroxide solutions.After discharging, removing thing 31 wherein can re-circulate to vaporizer 13.
Electrolysis cells comprises mercury cathode type electrolyzer 21, with 22 couplings of sodium amalgam splitter.Such electrolysis cells is well-known technology (J.S.Sconce, " Chlorine, its manufacture, Properties and uses " Reinhold Publishing Corporation, 1962, Pages 127 to 199).Electrolyzer 21 comprises the mobile mercury cathode on bottom of electrolytic tank (figure does not draw) of a level and the anode (not shown) of arranging towards the mercury film by form known, and is very short with latter's distance.Sodium chloride aqueous solution 23 contacts with anode with the mercury film and cycles through electrolyzer.After aqueous electrolysis decomposes, collect the aqueous solution 29 of chlorine 24, sodium amalgam 25 and sodium-chlor dilution.The per kilogram sodium amalgam contains just like the sodium between the 2.5-4 gram.It is sent to splitter 22, and the aqueous sodium hydroxide solution 20 reverse-flow circulations with the causticization unit is made in splitter 22, make sodium amalgam 25 contact (accompanying drawing is not shown) with graphite member with the aqueous solution 20.Sodium amalgam is owing to be decomposed gradually with the water reaction, and the result causes the generation of hydrogen 26.Collect mercury (or amalgam of sodium dilution) 27(and be circulated to electrolyzer 21) and aqueous NaOH alkali lye 28.

Claims (7)

1, the production method of sodium hydroxide lye is decomposed with containing dissolved sodium hydroxide water medium by this method sodium amalgam, it is characterized in that employed sodium hydroxide is produced by the lime treatment aqueous sodium carbonate.
2, in accordance with the method for claim 1, when it is characterized in that with the end of lime treatment sodium carbonate solution, collect rare sodium hydroxide solution, described dilute solution must be evaporated under the condition of control so that the concentrated solution per kilogram that forms contains the sodium hydroxide of 188.0-468 gram, described concentrated solution crystallisation by cooling goes out the sodium hydroxide hydrate, collect this hydrate and be heated to enough temperature and make it fusing, the sodium hydroxide hydrate processing of fusing of described sodium amalgam.
3, in accordance with the method for claim 2, it is characterized in that controlling evaporation so that make the concentrated solution of per kilogram contain the sodium hydroxide that 321-468 restrains, and spissated solution is through being cooled to temperature in 5-16 ℃ of scope.
4, in accordance with the method for claim 3, it is characterized in that controlling evaporation so that concentrated solution is had be lower than the sodium hydroxide weight content of 388.3g/kg.
5,, it is characterized in that the aqueous sodium carbonate that uses obtains by removing supercarbonate in the saturated sodium bicarbonate solution according to the described method of arbitrary claim among the claim 1-4.
6,, it is characterized in that the sodium amalgam per kilogram that uses contains the sodium of 1-5 gram according to the described method of arbitrary claim among the claim 1-5.
7, in accordance with the method for claim 6, it is characterized in that the sodium amalgam that uses is resulting by sodium chloride aqueous solution electrolysis in mercury-cathode cell.
CN 90107940 1989-08-17 1990-08-17 The production method of sodium hydroxide lye Pending CN1050056A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE8900880 1989-08-17
BE8900880 1989-08-17

Publications (1)

Publication Number Publication Date
CN1050056A true CN1050056A (en) 1991-03-20

Family

ID=3884285

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 90107940 Pending CN1050056A (en) 1989-08-17 1990-08-17 The production method of sodium hydroxide lye

Country Status (6)

Country Link
EP (1) EP0413385A1 (en)
CN (1) CN1050056A (en)
BR (1) BR9004064A (en)
CA (1) CA2023412A1 (en)
DD (1) DD297141A5 (en)
PT (1) PT94989A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1729326B (en) * 2002-12-19 2010-09-22 F.I.R.S.T.股份公司 Device for carrying out the programming of rotary dobbies in weaving machines
CN107973322A (en) * 2017-12-15 2018-05-01 沈阳市好太阳日用品加工厂 Environment-friendly novel sodium hydroxide powder agent
CN108314058A (en) * 2013-11-12 2018-07-24 索尔维公司 For handling a kind of method of sodium carbonate cleaning solution
CN114921663A (en) * 2022-06-14 2022-08-19 厦门钨业股份有限公司 Method for extracting tungsten from scheelite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2729133A1 (en) * 1995-01-11 1996-07-12 Solvay PROCESS FOR COPRODUCTION OF CALCIUM CARBONATE AND SODIUM HYDROXIDE

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH264595A (en) * 1945-12-20 1949-10-31 Solvay Process for the causticization of sodium carbonate.
US3321388A (en) * 1962-08-09 1967-05-23 Asahi Denka Kogyo Kk Process for coordinated operation of diaphragm and mercury cathode electrolytic cells
NO810316L (en) * 1980-03-03 1981-09-04 Uhde Gmbh PREVENTION FOR CONCENTRATION OF LOW PERCENTAGE OF NON-SOUND LODGE

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1729326B (en) * 2002-12-19 2010-09-22 F.I.R.S.T.股份公司 Device for carrying out the programming of rotary dobbies in weaving machines
CN108314058A (en) * 2013-11-12 2018-07-24 索尔维公司 For handling a kind of method of sodium carbonate cleaning solution
CN107973322A (en) * 2017-12-15 2018-05-01 沈阳市好太阳日用品加工厂 Environment-friendly novel sodium hydroxide powder agent
CN114921663A (en) * 2022-06-14 2022-08-19 厦门钨业股份有限公司 Method for extracting tungsten from scheelite
CN114921663B (en) * 2022-06-14 2023-11-21 厦门钨业股份有限公司 Method for extracting tungsten from scheelite

Also Published As

Publication number Publication date
CA2023412A1 (en) 1991-02-18
DD297141A5 (en) 1992-01-02
BR9004064A (en) 1991-09-03
EP0413385A1 (en) 1991-02-20
PT94989A (en) 1991-04-18

Similar Documents

Publication Publication Date Title
JP3671148B2 (en) Method for purifying lithium carbonate
US4036713A (en) Process for the production of high purity lithium hydroxide
US8691169B2 (en) Method for the production of battery grade lithium carbonate from natural and industrial brines
AU651359B2 (en) Chlorine dioxide generation from chloric acid
CA2071810C (en) Process for the production of chlorine dioxide
EP0498484B1 (en) Process for electrolytic production of alkali metal chlorate and auxiliary chemicals
CN109516479B (en) Preparation method of battery-grade lithium hydroxide
CN113249578B (en) Recycling treatment method of fluorine-containing waste generated by aluminum electrolysis and aluminum fluoride product
US4980136A (en) Production of lithium metal grade lithium chloride from lithium-containing brine
CN109592699A (en) The preparation method of LITHIUM BATTERY lithium hydroxide
RU2157338C2 (en) Method of production of high-purity lithium hydroxide from natural brines
CN102628105A (en) Method for comprehensively recycling and using baric waste slag in refined aluminum production process
JP3151182B2 (en) Copper electrolyte cleaning method
KR20120070841A (en) Method for preparing high purity lithium carbonate from brines
CN106006675A (en) Method for preparing lithium hydroxide monohydrate by using lithium chloride solution as raw material
CN1050056A (en) The production method of sodium hydroxide lye
EP0656083B1 (en) Reduction of chloride in pulping chemical recovery systems
AU6170594A (en) Process for recovering solid sodium bicarbonate from diaphragm cell
US3690845A (en) Crystallization of a metal chlorate from a chlorate-chloride containing solution
SE455706B (en) SET FOR PREPARATION OF ALKALIA METAL CHLORATE
CA2095062C (en) A method for removing impurities from an alkali metal chlorate process
CN1049874A (en) The production method of sodium hydroxide lye
US3681214A (en) Process for producing high-purity alkali hydroxides
CN103374662A (en) Device for recycling waste residues containing barium comprehensively during refined aluminum production process
CN114959306B (en) Method for recycling lithium from lithium precipitation mother liquor by closed cycle method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication